2-aminothiophene azo compounds



Unim tates Patent puma Z-ABHNGTEOPHENE AZO COlVIPOUNDS Edmund B. Towne,William H. Moore, and Joseph B. Dickey, Kingsport, Tenn., assignors toEastman Kodak glompany, Rochester, N. Y., a corporation of New ersey NoDrawing. Application August .12, 1955 Serial No. 528,132

11 Claims. (Cl. 260-152) This invention relates to new Z-aminothiophenecompounds, to new azo compounds prepared from said 2- aminothiophenecompounds, to the application of the new azo compounds to the art ofdyeing or coloring and to materials colored with the new azo compoundsofthe invention.

We have discovered that the new monoazo compounds having the formula:

wherein X represents a nitro group or an alkylsulfonyl group having 1 to4, inclusive, carbon atoms, Y represents an alkylsulfonyl group having 1to 4, inclusive, carbon atoms or a sulfonealkylamido group having 1 to4, inclusive,;carbon atoms and R represents an aniline couplingcomponent, a tetrahydroquinoline coupling component or a benzomorpholinecoupling component are useful for coloring a considerable number ofdifierent textile materials. They are useful, for example, for coloringcellulose alkyl carboxylic acid ester having 2 to 4 carbon atoms in theacid groups thereof textile materials, sulfone polyester textilematerials, nylon textile materials, wool, polyethylene terephthalate(Dacron) textile materials and polyacrylonitrile, especiallyacrylonitrile graft polymer, textile materials.

Ordinarily the azo compounds of our invention are applied by knowndyeing techniques to fabrics or fibers made of the aforesaid textilematerials. However, coloration can also be effected, for example, byincorporating the azo compounds into the spinning dope and spinning thefiber as usual. The azo compounds of our invention have varying utilityas dyes. The degree of utility varies, for example, depending upon thematerial being colored and the formula of the azo compound.

By cellulose alkyl carboxylic acid esters having two to four carbonatoms in the acid groups thereof, we mean to include, for example, bothhydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate,cellulose butyrate, cellulose acetate-propionate and celluloseacetatebutyrate.

The new monoazo compounds of our invention are prepared by diazotizing aZ-aminothiophene compound having the formula:

wherein X represents a nitro group or an alkylsulfonyl group having 1 to4, inclusive, carbon atoms and Y represents an alkylsulfonyl grouphaving 1 to 4, inclusive, carbon atoms or a sulfonealkylamido grouphaving 1 to 4, inclusive, carbon atoms and coupling the diazoniumcompound obtained with an aniline coupling component, atetrahydroquinoline coupling component or a homomorpholine couplingcomponent.

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An unusual characteristic of the azo compounds of our invention is thatthey yield dyeings wherein thecolor is much bluer than that obtainedwith the corresponding dyesprepared from a nitroalkylsulfonylanilinediazonium compound. in other words, the use of the new Z-aminothiophenecompounds of our invention causes a shift in color toward blue. The azocompounds of our invention yield violet to blue shades on the materialsindicated hereinbefore which have good fastness to light, washingyandsublimation, excellent gas fastness and which discharge to a pure white.Further, the dyeings obtained do not change color under artificiallight.

While our invention relates broadly to the new azo compounds having theformula numbered I, it relates more particularly to the azo compoundshaving the formulas:

wherein X represents a nitro group or an alkylsulfonyl group having 1 to4, inclusive, carbon atoms, Y represents an alkylsulfonyl group having 1to 4, inclusive, carbon atoms or a sulfonealkyiamido group having 1 to4, inclusive, carbon atoms, wherein R represents a hydrogen atom, analkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 2 to4 carbon atoms, an alkoxyalkyl group having 3 to 4 carbon atoms, acyanoalkyl group having 3 to 5 carbon atoms, a fi-acetoxyethyl group, acarbomethoxymethyl group, a carboethoxymethyl group, afi-carbomethoxyethyl group or a fi-carboethoxyethyl group, R representsan alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 2to 4 carbon atoms, an alkoxyalk 1 group having 3 to 4 carbon atoms, acyanoalizyl group having 3 to 5 carbon atoms, a fi-acetoxyethyl group, acarbomethoxymethyl group, a carboethoxymethyl group, afl-carbomethoxyethyl group, a fi-carboethoxyethyl group, a[3,,8-difiuoroethyl group, or a [3,13,5-trifiuoroethyl group, Qrepresents a hydrogen atom, a bromine atom, a chlorine atom, a methylgroup, an ethyl group, a methoxy group, an ethoxy group, an acetylaminogroup, an n-propionylamino group or an n-butyrylarnino group, Zrepresents a hydrogen atom, a methyl group, an ethyl group, a methoxygroup or an ethoxy group, R represents a hydroxyalkyl group having 2 to4, inclusive, carbon atoms, Q represents a hydrogen atom or a methylgroup and Q and Q each represents a hydrogen atom, a methyl group, amethoxy group, a chlorine atom, a bromine atom, a fluorine atom, anacetylamino grou a propionylamino group or a butyrylamino group.

2-amino-3,5-bis(methylsulfonyl)-thiophene. 2 amino- 3,5 -bisethylsulfonyl) -tniophene, 2-amino-3,5-bis (n-propylsulfonyl)-thiophene, 2 amino 3,5-bis (isopropylsulpropyl 7methyltetrahydroquinoline,

sulfonyl) -thiophene, 2 amino 3,5-bis(n-butylsulfonyl)- thiophene,Z-amino 3 nitro-S-methylsulfonylthiophene,2-amino-3rnitro-5-ethylsulfonylthiophene, 2 amino-3-nitro5-n-propylsulfonylthiophene, 2 amino 3 nitro=5 nbutylsulfonylthiophene,2-amino-3-nitro-5-sulfonem'ethylamidothiophene,2-amino-3-nitro-5-sulfonethylarnidothiophone, 2-amino-3nitro-5-sulfone-n-propylamidothiopherie and2-amino-3-nitro-5-sulfone-nbutylamidothiophene are illustrative of theZ-aminothiophene compounds used. in

the preparation of the azo compounds of our invention.

Illustrative of the alkyl groups represented by R and R are the methyl,the ethyl, the n-propyl, the isopropyl and the n-butyl groups.Similarly, the ,B-hydroxye'thyl, the fl-hydroxypropyl, they-hydroxypropyl, thefiyy-dihy- 'droxypropyl, the ,B-methyl-B,--dihydroxypropyl and the -hydroxybutyl groups are illustrative of thehydroxyalkyl groups R and R represent. illustrative of the alkoxy-'alkyl groups represented by R and R are the p-methoxyethyl and theB-ethoxyethyl groups. Similarly,'the ,8- cyanoethyl, the 'y-cyanopropyland the 6-cyanobuty1 group are illustrative of the cyanoalkyl groups Rand R represent.

Typical of the aniline coupling components used in the preparation ofthe azo compounds of'our invention are aniline, m-toluidine,m-anisidine, m-chloroaniline, 2- methoxy-S-chloroaniline,2,5-dimethoxyaniline, Z-methoxy 5 methylaniline,N-fi-hydroxyethylaniline, N-fi-hyare illustrative of thetetrahydroquinoline coupling comdroxypropylaniline, N 8,:-dihydroxypropylaniline, N--

hydroxypropylaniline, N-e-hydroxyb'utylaniline,N-fl-hydroxyethyl-o-chloroaniline, N-fi-hydroxyethyl-o-methoxyaniline,N-fl-cyanoethylaniline, N-B-methoxyethylaniline,N-fi-ethoxyethylaniline, N-B-carbomethoXyethyl-m-toluidine,N-B-carboethoxyethyl-m-chloroaniline, N,N-di-B-hydroxyethylaniline,N,N-di-fl-hydroXyethyl-m-chloroaniline,N,N-di-fi-hydroxyethyl-m-toluidine,N-ethyl-N-B,'y-dihydroxypropyl-m-toluidine,N-ethyl-N-(fi-methyl-dy-dihydroxypropyl)aniline, N-but'yl-N-(fi-sodiumsulfatoethyD- m-toluidine, :N-B-cyanoethyl-N-( S-sodiumphosphatoethyD-m-chloromiline,N-methyl-N-flq-dihydroxypropylm-toluidine, N-B-methoxyethyl-N-fi-dihydroxypropylm-toluidine, N,N-di-fi-hydroxyethyl-m-bromoaniline, N-ethyl-N-fi-hydroxybutylaniline, Nfi-hydroxyethyl-N-fl,fi,fitrifluoroethylaniline, N-p-hydroxyethyl-N-','y,- -trifluoropropylaniline,N-fi-hydroxyethyl-N-6j,fi-trifluorobutylani- -line,:N-B-hydroxyethyl-N-;8,B-difluoroethylaniline, N-'hydroXypropylN-'y;y-difiuoropropylaniline,N}3-hydroxyethyl-N-tgp,difiuoropropylaniline, N-p -dihydroxypropyh-N-'y,'y-difiuorobutylaniline, N-fi -dihydroxypropyl-N-5,6- ,difluoroamylaniline, N-methyl N ,8 hydroxyethyl-mbromoaniline,N,N-di-,B-hydroxyethyl 2,5 diethoxyaniline, 1 N,N-dieS-hydrOXyethyI-LS-dichloroaniline, N-npropyl N fl-hydroxyethylaniline,N-isopropyl-N-p-hydroxyethylaniline, N-n-butyl-N-B-hydroxyethylaniline,N- fl-hydroxyethyl-N-cyanoethylm -chloroaniline,N-B-hydroxyethyl-N-y-cyanopropylaniline, N-fl-carbomethoxy-'ethylaniline, N- -carb oethoxyethyl-N-fi-hydroxyethylaniline,N-p-carbomethoxyethyl-N-p-hydroxyethyl-m-chloroaniline,N-fi-hydroxyethyl-N-B-chloroallylaniline and N-hydroxyethyl-N-B-nitroethylaniline.

Tetrahydroquinoline, 1-ethyltetrahydroquinoline,l-flhydroxyethyltetra'hydroquinoline,- 1-3,'y-dih'ydroxypropyltetrahydroquinoline,1-B-methyl-fl,'y-dihydroxypropyltetrahydroquinoline, 1 'yhydroxypropyltetrahydroquino- 1ine,.1-6-hydroXybutyltetrahydroquinoline,l-fl-hydroxyethyl-2,7-dimethyltetrahydroquinoline,l-fi;ydihydroxypropyl-2,7-dimethyltetrahydroquinoline,'l-fi,'y-dihydroxypropyl 2 methyltetrahydroquinoline, l-fi -dihydroxy- V1-,8,'y-dihydroxypropyl-7-chlorotetrahydroquinoline, l,/9-'-dihydroxypropyl-7-bromotetrahydroquinoline, l-fi,y-dihydroxypropyl- 7fluorotetr'ahydroquinoline, l-fi-hydroxyethyl-7-ethyl--tetrahydroquinoline, l-fi-hydroxyethyl 7 methoxytetrahydroquinoline,l-fl-methyl 3, dihydroxypropyl-7 ethoxytetrahydroquinoline, 1 13methoxyethyltetrahydroquinoline, 1-ethoxyethyltetrahydroquinoline,l-fi-cyanm 1 line, l-'y,'y-difiuoropropylhen'zornorpholine,

ponents used in the preparation or" the azo compounds of our invention.7 ,k

Similarly, benzomorpholine, l etiiylbenzomorpholinc,l-B-hydroxyethylbenzomorpholine; l-figy-dihydroxypropylbenzomorpholine,1 B methyl-B,'y-dihydroXypropylbenzomorpholine, l yhydroxypropyl-benzomorpholine, i -d-hyd'roxybu'tylbenzomorpholine, 1-8-hydroXyethyl-2,7-. dimethylbenzomorpholine, l ,Byydihydroxypropyl-2,7- dimethyibenzomorpholine, 1 [3,7 dihydroxypropyl 2-methylbenzomorpholine, l43, -dihydroxypropyl-7-tnethyl benzomorpholine,1-,8,'y-dihydroXypropyl-7-chlorobenzomorpholine, 113,-dihydroxypropyl-7-bromobenzomorpholine, 1'- 5,dihydroxypropyl-7-fiuorobenzomorphodine,1-,B-hydroxyethyl-7-ethylbenzornorpholine,l-p-hydroXyethyl-7-methoxybenzomorpholine, l-B-methyl-pdihydroXypropyl-7;ethoxybenzomorpholine,l-fi-methoxyethylbenzomorpholine', 1"- ethoxyethylbenzomorpholine1-;8-cyanoethylbenzomorpholine, l-fl-carbomethoxyethylbenzomorpholine,l-B-carboethoxyethylbenzomorpholine,1-fi,fl,fl-trifluoroethylbenzomorpholine, l-6,6,6trifiuorobutylbenzomorpholine, l#3,B-difiuoroethylbenzornorpho-1-13,,8-difiuoropropylbenzomorpholine, 1-6,6-diiinoroamylbenzomonpholine, l B hydroxypropyl-2,7-dimcthylbenzomorpholine,1-B-sulfatoethylbenzomorpholine, l-fi-phosphatoethylbenzomorpholine,l-allylbenzomorpholine and 1-5- phosphonethylbenzomorphoiine areillustrative of the benzomorpholine coupling compounds used in thepreparation of the azo compounds of our invention.

a The monoazo compounds of our invention are dyes for fibers preparedfrom graft polymers obtained by'graft polymerizing acrylonitrile aloneor together with one or more other monoethylenic monomers with apreformed polymer. The preformed polymer can be a homopolymer (a olymerre ared by 01 'merization of a single mono- 'me'r) or it can be aninterpolymer such as a copolymer a polymer prepared by the simultaneouspolymerization in a single reaction mixture of two monomers) or aterpolymer (a polymer prepared by the simultaneous polymerization in asingle reaction mixture of threemonomers), or the like, andthe graftpolymers for which the dyes are particularly useful are those containingat least 5% by weight of combined acrylonitrile grafted to thepreformed'polymer molecule.

The graft polymers which can be dyed are thus polymers having directedplacement of the polymerized monomeric units in the graft polymermolecule as distinguished from the random distribution obtained ininterpolymers a single CH=C group and desirablya CH =C amate, acitraconamate, a maleamate, or a vinyl ester; or a '5 aninterpolymer oftwo or more of such monomers with each other or of atleast one of suchmonomers with one or more different monoethylenic monomers characterizedby a CH=C group such as styrene, acrylonitrile, substituted styrenes,vinyl or vinylidene chlorides, vinyl ethers, dialkyl maleates, alkenylketones, dialkyl fumarates, acrylic acid, methacrylic acid, substitutedacrylonitriles, furnaronitrile, ethylene and the like.

The graft polymerization is effected by polymerizing acrylonitrile or amixture ofacrylonitrile with any other monoethylenic monomer, includingany of the monomers enumerated hereinabove, with the preformed live ordead homopolymer or interpolymer whereby the acrylonitrile alone ortogether with another grafting monomer is combinedwith the preformedpolymer molecule to give a graft polymer containing from 5 to 95% byweight of combiried acrylonitnle.

:Insofar as graft polymers are concerned, the new azo compounds of ourinvention are of particular utility for dyeing fibers prepared from agraft polymer obtained by graft polymerizing acrylonitrile and anacrylamide or methacrylamide with apreformed copolymer of acrylonitrileand the same or different acrylamide or meth- .acrylamide.

U.'S. Patent 2,620,324, issued DecemberZ, 1952; U. S. Patent-2,649,434,issued August 18, 1953; and U. S. Patent 2,657,191, issued October 27,1953, disclose other typical graft polymers that can be dyed with thenew azo compounds of our invention.

Sulfone polyester textile materials that can be colored with the new azocompounds of our invention are disclosed in U. S. Patent 2,614,120,issued October 14, 1952. Additional sulfone polyester textile materialsthat can be colored with our new azo compounds are disclosed and claimedin copending Caldwell U. S. application Serial No. 313,061, filedOctober 3, 1952, now Patent No. 2,744,089. Anracrylonitrile graftpolymer textile materialaand a sulfone polyester textile material uponwhich the azo dyes have been applied are specifically describedhereinafter.

The following examples illustrate the compounds of our invention andtheir manner of preparation.

Example 1 6.76 grams of 2-acetamido-3,5-bis(chlorosulfonyl)- thiophene(JACS, 73, 615 [1951]) and 5.8 grams of sodium sulfite were stirredtogether in 20 cc. of water while 25% aqueous sodium hydroxide was addedat such a rate as to maintain a pH of 8-9. The temperature of thereaction mixture was maintained below 30 C. by means of an ice bath.After about 1 hour the reaction slowed and the reaction mixture was thengradually heated to 7 C. while maintaining a pH of 8-9 by addition of25% aqueous sodium hydroxide as needed. When the reaction mixture,containing the disodium salt of 2-acetamido-3,5- thiophenedisulfinicacid, reached the point that it could be stirred at 70 C. forl minuteswith no change in pH, it was neutralized with chloroacetic acid afterwhich 0.5

grams of potassium iodide were added and the reaction mixture heated toreflux. A neutral solution of 10.25 grams of sodium chloroacetate in 20cc. of water was added and the reaction mixture refluxed for 6 hours.The reaction mixture was then cooled and the 2-acetamido-3,5-bis(methylsulfonyl)-thiophene which separated as a solid was collectedon a filter and Washed Well with cold water. 264 grams of2-acetamido-3,5-bis(methylsulfonyl)-thiophene having a melting point of228 C.230 C. were thus obtained.

The 2-acetamido-3,5-bis (methylsulfonyl)-thiophene obtained as describedabove was refluxed in 100 cc. of 4 N hydrochloric acid until'solutionwas effected and then refluxing was continued for an additional halfhour. The reaction mixture was filtered while hot and the filtrate waschilled in an ice bath. The tan colored crystals of 2-amino-3,5-bis(methylsulfonyl)-thiophene which precipi- .6 tated werecollected on a 'filter and washed with water until neutral. A yield ofL55 grams was obtained. After recrystallization from water, the2-amino-3,5-bis(methylsulfonyl)-thiophene melted at 201.4 C. 5

Example 2 5.02 grams of an alkaline solution (pH 89) of the disodiumsalt of 2-acetamido-3,S-thiophenedisulfinic acid, prepared according tothe procedure described in Example 1, was heated at reflux for 12 hourswith 31 grams of ethyl iodide and sutficient ethyl alcohol to render thehot solution homogeneous. Upon completion of the refluxing the excessethyl iodide and ethyl alcohol were distilled otf and the2-acetamido-3,5-bis(ethylsulfonyl) thiophene which formed was recoveredfrom the reaction mixtureby extraction with ethyl ether. The ethyl etherextract was dried over anhydrous sodium sulfate and the ethyl etherevaporated.

The 2-acetamido-3,5-bis(ethylsulfonyl)-thiophene prepared as describedabove was hydrolyzedwith 4 N hydrochloric acid in accordance with theprocedure described in Example 1 to obtain 2 grams of 2-amin0-3,5- bisethylsulfonyl -thiophene.

Example 3 Bythe use of 34 grams of n-propyl iodide in place of ethyliodide in Example 2, 2-amino-3,5-bis(n-propylsulfonyD-thiophene isobtained.

Example 4 2-amino-3,5-bis(n-butylsulfonyl)-thiophene was prepared inaccordance with the procedure described in Example 2 except that 36.8grams of n-butyl iodide was used in place ofethyl iodide and thereaction mixture was heated at reflux for 18 hours instead of 12 hours.A yield of 2.8 grams was obtained.

Example 5 21.7 grams of 5-chlorosulfonyl-2-chlorothiophene (Annalen,532, 264 [1937]) and 13.9 grams of sodium sulfite were stirred togetherin 100 cc. of water while 25% aqueous sodium hydroxide was added at sucha rate as to maintain a pH of 8-9. The temperature of the reactionmixture was kept under 30 C.-by means of an ice bath. After about 1hour, the reaction slowed and the reaction mixture was then graduallyheated to 70C. while maintaining a pH of 8-9 by addition of 25% aqueoussodium hydroxide as needed. When the reaction mixture, containing thesodium salt of 2-chlorothiophene- 5-sulfinic acid, reaches the pointthat it canbe stirredat 70 C. for 15 minutes with no change in pH, itwas neutralized with chloroacetic acid (approximately 0.6 gram) and 2grams of potassium iodide were added. The reaction mixture was thenheated to reflux and a solution of 13.1 grams of sodium chloroacetateand 2.64 grams of chloroacetic acid in 50 cc. of water was addeddropwiseover a period of 3 hours. After this addition was completed,refluxing was continued for 4 hours longer. The reaction mixture wasallowed to cool following which theQ-chloro- 5-methylsulfonylthiopheneformed in the reaction was extracted with ethyl ether. The ethyl etherextract was tied over Drierite and the ether evaporated.Uponrecrystallization from cyclohexane 12 grams of 2-chloro -5-methylsulfonylthiophene having a melting point of 72 C.-75 C. wereobtained.

53.95 grams of 2-chloro-5-methylsulfonylthiophene were added portionwiseover a period of 1 /2. hours toan ice-cooled mixture of concentratedsulfuric acid (specific gravity 1.84, 96%) and fuming nitric acid(specific gravity 1.5, About half way through the addition a white solidbegan to separate from the reaction mixture. After the addition of the2-chloro-5-methylsulfonylthiophene was completed, the reaction mixturewasstirred at ice bath temperature for l and /2 hour, then drownedinrice, filtered and the product recovered-on the filter-was washed coolwater until neu tr fonyl)thiophene is obtained.

. reaction mixture by extraction with ethyl ether.

tallized from water containing charcoal to obtain 9.5

grams of 2-amino-3-nitro-5-methylsulfonylthiophene melt- Example 6 Bythe use of 34 grams of isopropyl iodide in place of ethyliodideinExample 2, 2-amino-3,5-bis(isopropylsul- Example 7 I 7 An alkaline,aqueous ethyl alcohol solution (pH 89) of 20.5 grams of the sodium saltof 2-chlorothioPhene-5- Upon recrystallining the a sulfinic. acidprepared as described in the first part of Example 5 was heated atreflux for 12 hours with 83 grams of ethyl iodide. The excess ethyliodideand ethyl alcohol were distilled off and theZ-chloro-S-ethylsulfonylthiophene-formed by the reaction was separatedfrom the The ethyl ether extract was dried and the ethyl ether distilledoff, to yield 12.7 grams of 2-chloro-S-ethylsulfonylthiophene;

' The 12.7 grams of 2-chloro-S-ethylsulfonylthiophene prepared asdescribed above were nitrated by adding it portionwise overa period of 1/2 hours to a mixture of 15 grams of concentrated 96% sulfuric acid and5.2 grams of 90% nitric acid, cooled in an ice bath. After addition ofthe- 2-chloro-5-ethylsulfouylthiophene was complete,

stirring was continued for 1 /2 hours and then the reaction mixture wasdrowned on ice, filtered, and the product recovered on the filter waswashed well with water and dried. 13.5 grams of2-chloro-3-nitro-5-ethylsulfonylthiophene were recovered as a whitecyrstalline solid.

The 13.5 grams of 2-chloro-3-nitro-5-ethylsulfonylthiophene prepared asdescribed above were dissolved in 400 cc. of absolute ethyl alcohol andaminated by bubbling anhydrous ammonia into the reaction mixture for 2hours 'while mainaining the reaction mixture at 70 C. and stirring. Thenthe reaction mixture was concentrated to onethird its volume and cooled.A reddish soild precipitated and was recovered by filtration. Thereddish solid was recrystallized from water to obtain 6.4 grams of2-amino 3-nitro-5-ethylsulfonylthiophene.

Example 8 By use of 85 grams of n-propyl iodide in place of ethyliodidein Example 7, 2-amino-3-nitro-5-n-propylsulfonylthiophene isobtained. a

7 Example 9 7 By the use of 92 grams of n-butyl iodide in place of ethyliodide in Example 7, 2.-amino-nitro-5-n-butylsulfonylthiophene isobtained. s

' Example 10 V 24.8 grams of 2-chloro-3-nitro-5-chlorosulfonylthiophene(JACS, 1948, page were dissolved in 60 cc. of acetone and the solutionresulting was stirred at 0 C.-5 C. while 36 grams of a 33% aqueoussolution of .ethylarnine were added over a period of about 1 and /2hour. After strirring for-an additional half hour at 0C., the reactionmixture was poured'into 400 cc. of

ice wat er. On standing, the oil which separated became solid. 17.8grams of crude 2-chloro-3-nitro-5-sulfonethyl amidothiophene were" thusobtained by recovery of the solid from the ice water. Uponrecrystallization from germs-6 aqueous ethylalcohol a. purified productmelting at 70 C.- 73 C. was obtained. 7 a i q '4 grams of purified2-chlorofi-nitro-5-sulfonethyl amidothiophene obtained as describedabove was refluxed for 1 hour with 14 cc. of concentrated aqueousammonium hydroxide in 50 cc. of ethyl alcohol. After refluio' ing wascomplete, the reaction mixture was concentrated to one-third its volumeand the ammonium chloride which precipitated was removed by filtration.Upon evapora tion of the remaining solution to dryness 3.1 grams of2-amino-3-nitro5-sulfonethylamidothiophene were ob tained as an oilwhich solidified on standing.

Example 11 By the use of an equivalent amount of methylamine,npropylamine and n-butylamine, respectively, for ethyl amine in Example10, 2-amino-3-nitro-5-sulfonemethy1- amidothiophene, 2 amino 3- nitroS-sulfone-n-propyh amidothiophene and 2-amino-3-nitro-5-sulfone-n-butyl+amidothiophene, respectively, are obtained.

Example 12 Nitrosylsulfuric acid was prepared by adding 1.52 grams ofsodium nitrite portionwise to 10 cc. of concentrated sulfuric acid, withstirring, and allowing the temperature to rise to C. The solution thusobtained was then cooled to 5 C. and a mixture consisting of 3 cc. ofpro picnic and 17 cc. of acetic acid was added dropwis'e',

with stirring,'whi1e allowing the temperature to rise to 15 C. and thenkeeping it there during the addition of the acid mixture. The reactionmixture thus obtained was then cooled to 0 C.-5 C. and 5.61 grams Of '2'amino-3,5-bis (methylsulfonyl)-thiophene were added per tionwise whilestirring, after which'a mixture of 3 cc;

of propionic' acid and 17 'cc. of acetic acid was added while keepingthe temperature of the reaction mixture at 0 C.5 .C.. The reactionmixture was then stirred at 0 C.5 for 2 hours and the excess sodiumnitrite present was destroyed by adding 1 gram of urea. A cleardiazonium solution of 2-amino-3,5-bis(methylsulfonyD- thiophene wasobtained by the foregoing procedure. 1

10 cc. of the diazonium solution prepared as described in the precedingparagraph were added, with stirring, to a solution of 0.84 gram ofN-ethyl-N-[L' -dihydroxypropylm-toluidiue in 7 cc. of 10% aqueoussulfuric acid cooled to 0 C. at such a rate that the temperatureremainedat 0 C.5 C." The coupling reaction which takes place was allowedto proceed for 15 minutes and then the reaction mixture was drowned in200 cc. of water with stirring.

After the drowned reaction mixture had stood for about 1 hour, the dyecompound which precipitated wasrecovered by filtration, washed withWater until neutral and dried. 1.28 grams of thedye compound having theformula: V

H(|I|}C-SOCH3 05H; onions-cg /CN=N N\ S I onionomon were thus obtained.It dyes the textile materials named hereinbefore such as celluloseacetate, nylon, sulfone' polyester and acrylonitrile graft polymertextile materials,

for example, as well as wool, brightviolet shades. The

dyeings on these materials have good light and gas fast ness and underartificial light there is no change in color toward red, The dyeingsprepared on cellulose acetate fabric with this dye compound gave sharp,white dis charge prints.

Example 13 By the use of 0.78 gram of N, N-di-fl-hydroxyethyl-mtoluidinein place of N-ethy1-N-B,- -dihydroxypropyl-mtoluidine .in'Ex'ample 12,1.39 .grarns of 'a dye' compound which colored cellulose acetate fabricbright violet shades 9 were obtained. The color of the dyed fabric didnot shift toward red under artificial light.

Example 14 By the use of 0.94 gram of N-fl,' -dihydroxypropyl-2,7-dimethyltetrahydroquinoline in place ofN-ethyl-N-Bqdihydroxypropyl-m-toluidine in Example 12, 1.47 grams of adye compound were obtained in the form of a dark powder. The dyecompound obtained colored cellulose acetate, nylon and sulfone polyesterfabrics, for example, deep blue-violet shades.

Example 15 4.44 grams of 2-amino-3-nitro-5-methylsulfonylthiophene werediazotized with nitrosylsulfuric acid in aceticpropionic acid inaccordance with the proceduredescribed in Example 12 for thediazotization of 2 arnino-3,5-bis- (methylsulfonyl)-thiophene. A cleardiazonium solution was obtained.

10 cc. of the diazonium solution prepared in the preceding paragraphwere coupled with 0.84 gram of N453 dihydroxypropyl N ethyl m toluidine.Diazotization, coupling and recovery of the dye compound formed werecarried out in accordance with the general procedure described inExample 12. 1.02 grams of dye were obtained. The dye compound obtainedcolored cellulose acetate a bright blue shade and likewise dyed wool,nylon and sulfone polyester fabrics blue shades. The dyeings obtainedhad good fastness to light and gas and gave sharp white dischargeprints. V

Example 16 5.02 grams of 2-amino-3-nitro-5-sulfonethylamidothiophenewere diazotized with nitrosylsulfuric acid in aceticpropionic acid inaccordance with the procedure described in Example 12 for thediazotization of '2 amino-3,5-bis- (methylsulfonyl)-thiophene. A cleardiazonium solution was obtained.

10 cc. of the diazonium solution prepared as described in the precedingparagraph were coupled with 0.84 gram of N ethyl N 1 ,7 dihydroxypropylm toluidine. Coupling and recovery of the dye compound formed werecarried out in accordance with the general procedure described inExample 12. 1.2 grams of a dye compound which colors cellulose acetatefabrics blue shades having good fastness to light and gas Were obtained.The dyeings discharged to a sharp clear white and were unchanged underartificial light.

Example 17 4.4 grams of 2-amino-3-nitro-S-methylsulfonylthiophene werediazotized with nitrosylsulfuric acid in acetic-propionic acid inaccordance with the procedure described in Example 12 for thediazotization of 2-'ar nino-3,5-bis- (methylsulfonyl)-thiophene. A cleardiazonium solution was obtained.

10 cc. of the diazonium solution prepared in the preceding paragraphwere coupled with 0.47 gram of N 8,dihydroxypropyl-2,7-dimethyltetrahydroquinoline. Coupling and recoveryof the dye compound formed were carried out in accordance with thegeneral procedure described in Example 12. 0.31 gram of a dye whichcolors the materials named hereinbefore such as cellulose acetate, nylonand polyethylene terephthalate, for example, bright blue shades wereobtained. The dyeings on cellulose acetate fabrics gave sharp whitedischarge prints.

/ Example 8 By the use of 0.41 gram ofN-fi-hydroxyethyl-ZJ-dimethyltetrahydroquinoline in ,place ofN-B,'y-dihydroxy-- 10 Example 19 By the use of 0.44 gram of N-p,y-dihydroxypropyl-7- te y roq ne i P1352? .Q .N-firrfllhXiIQEpropyl-2,7-dimethyltetrahydroquinoline in Example 1,7, a dye whichcolors cellulose acetate light blue shades was obtained as a darkpowder.

Example 20 5 cc. of the diazonium comp oundprepared as described inExample 12 were coupled with 0.46 gram of N-i'y-dihydroxypropyl-S-methylbenzomorpholine. Coupling and recovery ofthe dye compound formed were carried out in accordance with theprocedure described in Example 12.

0.72 gram of dye compound were obtained as .a dark powder. The dyecompound thus obtained colored cel-- lulose acetate, wool, nylon,sulfone polyester and p olyethylene terephthalate textile fabricsblue-green shades. The dyeings obtained discharged to-apure White.

Example 21 a i0 cc. of the diazonium solution prepared as described inExample 17 were coupled with 0.86 gram of N,N-di--hydroxyethyl-m-chloroaniline. Coupling and recovery of the dye compoundformed were carried out in accordance with the general proceduredescribed in Example 12. The dye compound obtained coloredcelluloseacetate, nylon and sulfone polyester fabrics, for example,blue-violet shades having good fastness to light andlgas.

Example 23 10 cc. of a diazonium solution preparedas described inExample 12 were coupled with 0.82 gram of N-B-hydroxyethyl-2,7-dimethyltetrahydroquinoline. Coupling and recovery ofthe dye compound formed were carried out in accordance with the generalprocedure described in Example 12. The dye compound obtained coloredcellulose acetate, nylon and sulfone polyester fabrics, for example,blue-violet shades having good fastness to light and gas.

Example 24 10 cc. of a diazonium solution prepared as described inExample 12 were coupled with 0.95 gram of N-{Bdihydroxypropyl-2,7-dimethylbenzornorpholine. Coupling and recovery ofthe dye compound formed were carried out in accordance with the generalproceduredescribed in Example 12. The dye compound obtained coloredcellulose acetate, nylon, polyethylene terephthalate and sulfonepolyester fabrics blue shades. The dyeings ,obtained had good fastnessto light andgas. i

The following tabulation further illustrates the compounds includedwithin the scope of our invention together with the color they produceon cellulose acetate. The compounds indicated below are prepared bydiazotizing the amines listed under the heading Amine" and coupling thediazonium compounds obtained with .the compounds specified in the columnentitled fCqupling component. The diazoti zation and coupling reactionsmay, for example, be carried out following the general procedureindicated hereinbefore.

. allowed to level oif at 37-39 C.

' amide was soluble in N,N-dimethylformamide.

' ing mixture is dispersed in water.

heated to a temperature,"approximating C. and the textile material to bedyed is I immersed in the dye bath, following which the tempera-.textile material is removed ture. agitated until a homogeneous solutionof dope containing by, weight of'the copolymer resulted.

30.7 g. (3.07 g. of copolymer) of the above-prepared solution or dope ofthe copolymer were placed in a jacketed reactor provided with anagitator and heat exchanger. 114 cc. of water, 0.58 g. of 85% phosphoricacid, 0.1 g. of potassium persulfate, 0.17 g. of potassiummetabisulfite, 0.1 g. of tertiary dodecyl mercaptan and 0.56 g. of

30% solution in water of N -methyl methacrylamide and the mixtureheated, with stirring, to 35 C. and then After the heat ofpolymerization had been removed and when the conver sion of theacrylonitrile to polymer had reached 96% or more, which is usuallyaccomplished in a period of about 12 hours, the temperature wasraised-to 90 C. The mother liquor was' removed by centrifuging thepolymerization mixture,

There were then added 10 g. of acrylonitrile,

. instances special dyeing techniques,

In the case of certain the acrylonitn'le graft poly- 1 mers describedhereinbefore it is necessary to dye at the boil for an extended periodof time. Instances may 1 be encountered where the fiber is notsatisfactorily colored by the dyeing procedure just described. lnflthesesuch asthe use of pressure, for example, developed by the art for thecoloration of materials difficult to color may be employed.

the polymer precipitate being reslurr'ied twice with water andcentrifuged to a 70% The cake was dried under vacuum at The over-allyield of modi- After moisture cake. 80 C. in an agitated dryer. fiedpolyacrylonitrile product was over 90%.

was stored in a moisture proof container.

The acrylonitrile graft polymer prepared as above and PREPARATION OFSULFONE containing about 18% an extensibility the drafting and hammermilling, the dry powder, now ready for spinning, J

Widely varying amounts of dye can be used in the dyeing operation. Theamount of dye used .can be, for example, /3 to 3% (by weight) of that ofthe textile material although lesser or greater amounts of the dye canbe employed. 7 V j V 7 V The following example illustrates onesatisfactory way in which the fibers, of the acrylonitrile graftpolymers can be dyed using the azo compounds of our invention. 16milligrams of dye are ground with an aqueous solution of sodium ligninsulfonate until well dispersed or alternately the dye can be dissolvedin 5 cc. of hot Cellosolve. The dispersion or solution, as the-case maybe, is then poured into 150 cc. of Water to which a small amount of asurface-active agent such as Igepon T 1'1 s3- O- H3 1 ZH SQ N f Nekal BX(sodium alkylnaphthalene;sulfonate) orOrvus (sodium lauryl'sulfate-type)has'been added. The dye bath is then brought to. the desired temperatureand 5 grams of well wet-out fibers of the graft polymer are addedthereto. Dyeing is continued until the-proper shade is reached; Fromtime to time'throughout the dyeing operation, the material is workedtojpromote even dyeingf Ac'rylonitrile' graft polymers including thoseof the type specifically described hereinbefore are described andreornnrsuuin POLYMER One hundred g. p,p'-sulfonyl dibenzoic acidethyliester and 40 g. 1,5-pentanediol were placed in a reaction ves 'selequipped with a stirrer, a short distillation column,

and an inlet tube for purified nitrogen. Five col of ethanol containing0.4 g.'Ti (OC I-I was added and the mixture was heated at ISO-200 C.with stirring.-

After 1 hour, the distillation of ethyl alcohol ceased, and thetemperature was raised to 280-285 C. where it was held for 20 minutes..A vacuum of 0.5 to 1.0 mm.

was applied for 1 hour while the temperature was rnain- I tained at280285 C. A colorless product having an inherent viscosity of 0.80-0.90in. 60% phenol-40% tetrachlorethane solution was obtained. Fibers pulledfrom the melt and cold-drawn 400500% show a sticl ing temperature of240-250 C. The product is also useful for films and sheets.

The monoazo compounds of our invention can be applied to cellulosealkyl-carboxylic acid esters having 2 to 4 carbon atoms in the acidgroups thereof, nylon,

acrylonitrile graft polymers, sulfone polyester and polyethyleneterephthalate textile materials inthe form of an aqueous dispersion andare ordinarily so applied- To illustrate, the dye compound is finelyground with a dispersing agent such as sodium lignin sulfonate, Turkeyred oil, soap, or an oleyl glyceryl sulfate and the result- The dye baththus prepared ,is 45 C.-55

ture is gradually raised to C. C. and maintained with-an aqueoussoapsolution, rinsed well with water and dried,

' at this temperature until dyeing is complete, usually oneto 4 carbonatoms, a

, claimed in Coover U. S. applicationSerialNo. 408,012,

filed February 3, 1954.

wherein Xjrepresents a member selected from the group 7 7 consisting" ofanitro group and an alkylsulfonyl group having 1 to 4, inclusive, carbonatoms, Y represents a member selected from the group consisting ofanfalkyL sulfonyl group having 1 m 4, inclusive, carbon atoms and asulfonealkylamido group having I to ,4, inclusive,

carbon atoms and R represents a member selected from the groupconsisting of an aniline jcbii ung'cempsnem, a tetrahydroquinolinecoupling component anda- -benzomorpholine coupling component. i Y

2. The azo compounds having theformular' 7 l r R:

Q 7 H U V V wherein R represents a member selected from the groupconsisting of a hydrogen atom, an alkyl grouphaving 1 hydroxyalkyl grouphaving 2 to 4 carbon atoms, an alltoxyalkyl g roup havin'g' 3 to'4'carbon atoms, a cyanoalkyl group having 3 to 5 carbon, atoms, afl-acetoxyethyl group, a carbomethoxymethyl group, 'acarboethoxymethyllgroup, a fi-carbomethoxyethyl group and aB-carboethoxyethyl group, selected from the group consisting of an alkylgroup having 1 to 4 carbon atoms, a hydroxyalkyl group having 2 to 4carbon atoms, an alkoxyalkyl group having'3 to 4 carbon atoms, acyanoalkyl group having 3 to 5 carbon atoms, .a .p-acetoxyethyl group, acarbomethoxymethyl group, a carboethoxymethy1 group, a fi-carbomethoxy-,ethyl group, a ,B-carboethoxyethyl group, a 13,)8-difluoroethyl groupand a fi fi s-trifluoroethylgroup,Q represents R; represents .a member17 a member selected from the group consisting of a hydrogen atom, abromine atom, a chlorine atom, a methyl group, an ethyl group, a methoxygroup, an ethoxy group,

an acotylamino group, an n-propionylomino group and wherein R representsa hydroxyalkyl group having 2 to 4, inclusive, carbon atoms, Qrepresents a member selected from the group consisting of a hydrogenatom and a methyl group, Q and Q each represents a member selected fromthe group consisting of a hydrogen atom, a methyl group, a methoxygroup, a chlorine atom, a bromine atom, a fluorine atom, an acetylaminogroup, a propionylamino group and a butyrylamino group, X represents amember selected from the group consisting of a nitro group and analkylsulfonyl group having 1 to 4, inclusive, carbon atoms and Yrepresents a member selected from the group consisting of analkylsulfonyl group having 1 to 4, inclusive, carbon atoms and asulfonealkylamido group having 1 to 4, inclusive, carbon atoms.

4. The azo compounds having the formula:

wherein R represents a hydroxyalkyl group having 2 to 4, inclusive,carbon atoms, Q represents a member selected from the group consistingof a hydrogen atom and a methyl group, Q and Q each represents a memberselected from the group consisting of a hydrogen atom, a methyl group, amethoxy group, a chlorine atom, a bromine atom, a fluorine atom, anacetylamino group, a propionylamino group and a butyrylamino group, Xrepresents a member selected from the group consisting of a nitro groupand an alkylsulfonyl group having 1 to 4, inclusive, carbon atoms and Yrepresents a member selected from the group consisting of analkylsulfonyl group having 1 to 4, inclusive, carbon atoms and asulfonealkylamido group having 1 to 4, inclusive, carbon atoms.

5. The azo compounds having the formula:

wherein R represents a member selected from the group consisting of ananiline coupling component, a tetrahydroqumollne coupling component anda benzomorpholine coupling oomponoot.

6. The azo compounds having the formula:

H("'JCNO2 CH3OZSC CN=NR HC-C-SOzCHa C2 5 CH2$HCH2OH 8. The azo compoundhaving the formula:'

HCC-NO2 C2115 CHMIIHCHEOH 9. The azo compound having the formula:

HCCNO2 C2115 H II II GzH NO:SC C-N=N N S ornonomon CH: i

10. The azo compound having the formula: on omoHomorr H CH3- HO-CN0z Con o s ('2 i'JNN 11. The azo compound having the formula:

(|)H CHzCHCHrOH H CH3' n -o-solons 0 CH3 CH: CH 0 s0 0 N=\I- ReferencesCited in the file of this patent UNITED STATES PATENTS 2,443,598 CheneyJune 22, 1948 2,625,541 Long Jan. 13, 1953 2,625,552 Long Jan. 13, 19532,717,254 Miller Sept. 6, 1955

1. THE AZO COMPOUNDS HAVING THE FORMULA: